2D/2D耦合构建ZnIn2S4/TiO2异质结及其增强的光催化还原CO2性能

doi:10.15541/jim20250097

无机材料学报 ›› 2026, Vol. 41 ›› Issue (2): 177-185.DOI: 10.15541/jim20250097 CSTR: 32189.14.jim20250097

2D/2D耦合构建ZnIn₂S₄/TiO₂异质结及其增强的光催化还原CO₂性能

朱建华¹^,²(), 杨鑫¹, 茹凌杰¹

1.安徽工业大学冶金减排与资源综合利用教育部重点实验室, 马鞍山 243002
2.安徽工业大学低碳冶金与固废资源化利用安徽省重点实验室, 马鞍山 243002

收稿日期:2025-03-07 修回日期:2025-08-13 出版日期:2025-08-26 网络出版日期:2025-08-26
作者简介:朱建华(1978-), 男, 副教授. E-mail: zjianhua@ahut.edu.cn
基金资助:
安徽省自然科学基金(2308085MB66);安徽省重点研发项目(2022h11020028)

2D/2D Coupled ZnIn₂S₄/TiO₂Heterojunction and Its Enhanced Photocatalytic Reduction of CO₂

ZHU Jianhua¹^,²(), YANG Xin¹, RU Lingjie¹

1. Key Laboratory of Metallurgical Emission Reduction & Resources Recycling, Ministry of Education, Anhui University of Technology, Maanshan 243002, China
2. Anhui Key Laboratory of Low Carbon Metallurgy and Solid Waste Resource Utilization, Anhui University of Technology, Maanshan 243002, China

Received:2025-03-07 Revised:2025-08-13 Published:2025-08-26 Online:2025-08-26
About author:ZHU Jianhua (1978-), male, associate professor. E-mail: zjianhua@ahut.edu.cn
Supported by:
Natural Science Foundation of Anhui Province(2308085MB66);Key Research and Development Project of Anhui Province(2022h11020028)

摘要/Abstract

摘要：

二氧化钛(TiO₂)作为一种典型的光催化材料, 因其优异的化学稳定性、无毒性和低成本等优势, 在环境治理和能源转换领域得到了广泛应用。然而, 较宽的带隙结构导致其只能吸收紫外光, 而且块体材料中光生电子-空穴对的严重复合制约了量子效率。本研究采用水热法构筑了一种新型2D/2D耦合的ZnIn₂S₄(ZIS)@TiO₂复合材料。该异质结构由超薄TiO₂纳米笼与ZIS纳米片复合而成, 具有独特的中空核壳形貌。复合20 mg TiO₂纳米笼的ZIS-T20催化剂在400~720 nm宽波长范围内展现出显著增强的光吸收能力。在内建电场的作用下, 光生电子无法从ZIS的导带(CB)向TiO₂的CB迁移, 而空穴从ZIS的价带(VB)转移至TiO₂的VB却不受阻碍, 这种空间分离效应使得ZIS中保留了具有较高还原电位的电子, 克服了传统I型异质结还原电势降低的固有缺陷。在光催化CO₂还原(PCR)性能测试中, ZIS@TiO₂的催化性能得到显著提升, CO和CH₄的生成速率分别达到58.87和12.03 μmol·g^-1·h^-1, 其中CO选择性高达83.03%, CO的生成速率较纯ZIS和TiO₂分别提高了6.15倍和1.96倍。该工作不仅为设计高效2D/2D异质结光催化剂提供了新思路, 也为深入理解界面电荷转移机制提供了重要参考。

关键词: 2D/2D耦合, TiO₂纳米片, 光催化CO₂还原, 异质结, ZnIn₂S₄

Abstract:

As a typical photocatalytic material, titanium dioxide (TiO₂) has been widely applied in environmental remediation and energy conversion due to its excellent chemical stability, non-toxicity and low cost. However, its wide bandgap structure restricts light absorption to ultraviolet wavelengths, and severe recombination of photogenerated electron-hole pairs in bulk materials limits quantum efficiency. Here, a hydrothermal method was used to construct a novel 2D/2D coupled ZnIn₂S₄ (ZIS)@TiO₂ composite material. This heterojunction consists of ultrathin TiO₂ nanocages composited with ZIS nanosheets, exhibiting a unique hollow core-shell morphology. ZIS-T20 catalyst with composite 20 mg TiO₂ nanocages demonstrates significantly enhanced light absorption across a broad wavelength range of 400-720 nm. Under influence of the built-in electric field, photo-generated electrons cannot migrate from conduction band (CB) of ZIS to that of TiO₂, whereas the transfer of holes from valence band (VB) of ZIS to that of TiO₂ proceeds unimpededly. This spatial separation effect preserves electrons with high reduction potential in ZIS, overcoming inherent drawback of reduced redox capability in conventional type-I heterojunctions. In photocatalytic CO₂ reduction (PCR) reaction, ZIS@TiO₂ exhibits improved performance, achieving CO and CH₄ production rates of 58.87 and 12.03 μmol·g^-1·h^-1, respectively, with CO selectivity as high as 83.03%. Compared to individual components, the CO yield is 6.15 and 1.96 times higher than that of pristine ZIS and TiO₂, respectively. This work not only provides a new strategy for designing efficient 2D/2D heterojunction photocatalysts, but also offers valuable insights into understanding interfacial charge transfer mechanisms.

Key words: 2D/2D coupling, TiO₂ nanosheet, photocatalytic CO₂ reduction, heterojunction, ZnIn₂S₄

中图分类号:

TQ426

朱建华, 杨鑫, 茹凌杰. 2D/2D耦合构建ZnIn₂S₄/TiO₂异质结及其增强的光催化还原CO₂性能[J]. 无机材料学报, 2026, 41(2): 177-185.

ZHU Jianhua, YANG Xin, RU Lingjie. 2D/2D Coupled ZnIn₂S₄/TiO₂Heterojunction and Its Enhanced Photocatalytic Reduction of CO₂[J]. Journal of Inorganic Materials, 2026, 41(2): 177-185.

图/表 9

图1 材料的形貌结构

Fig. 1 Morphologies and microstructures of materials (a) SEM and (b) TEM images of 125-Tyr; (c) SEM and (d) TEM images of ZIS; (e) SEM, (f) TEM and (g) HRTEM images of ZIS-T20; (h) Line scan of ZIS-T20; (i-m) Distributions of elements for ZIS-T20. Colorful figures are available on website

图2 材料的XRD图谱(a)和FT-IR光谱图(b)

Fig. 2 (a) XRD patterns and (b) FT-IR spectra of materials Inset in (b) indicates the local magnification of ZIS. Colorful figures are available on website

图3 材料的物化性能

Fig. 3 Physical and chemical properties of materials (a) N2 adsorption-desorption curves with inset showing the corresponding pore size distributions; (b) CO2 adsorption curves; (c) CO2-TPD profiles; (d) UV-Vis diffuse reflectance spectra with inset showing (αhv)2 versus hv plots; (e, f) Mott-Schottky spectra of (e) ZIS and (f) 125-Tyr. Colorful figures are available on website

图4 准原位XPS图谱

Fig. 4 Quasi-in situ XPS spectra (a) Total spectra; (b) Zn2p, (c) In3d, (d) S2p, (e) Ti2p, and (f) O1s XPS spectra of ZIS-T20 before and under light irradiation

图5 材料的光电性能测试

Fig. 5 Photoelectric performance tests of materials (a) Steady-state PL spectra; (b) TRPL spectra; (c) Transient photocurrents; (d) EIS plots. Colorful figures are available on website

图6 材料的光催化性能测试

Fig. 6 Photocatalytic performance tests of materials (a) Photocatalytic CO2 reduction rates of different samples; (b) Photocatalytic products of ZIS-T20 for 8 h; (c) Photocatalytic cycle tests of ZIS-T20; (d) Isotope trace of photocatalytic products

表1 相关文献报道的催化剂及其光催化效果

Table 1 Reported catalysts and their photocatalytic effects

Material	Photoreactor condition	Product	Production rate/ (μmol·g⁻¹·h⁻¹)	Ref.
Porous TiO₂ (B)	300 W Xe-lamp	CH₄CH₃OH	0.23 0.08	[40]
TiO₂ anatase	90 mW/cm² solar simulator	CO	0.55	[41]
Pure ZnIn₂S₄	300 W Xe-lamp	CO CH₄	1.56 0.026	[42]
3D-ZnIn₂S₄/TiO₂	300 W Xe-lamp	CH₄	1.135	[43]
2D/2D ZIS-T20	300 W Xe-lamp	CO CH₄	58.87 12.03	This work

图7 ZIS-T20在PCR过程中的原位红外漫反射图谱

Fig. 7 In situ DRIFTS spectra of ZIS-T20 during PCR reaction

图8 ZIS-T20的PCR原理图

Fig. 8 Schematic diagram of ZIS-T20 for PCR

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2D/2D耦合构建ZnIn₂S₄/TiO₂异质结及其增强的光催化还原CO₂性能

2D/2D Coupled ZnIn₂S₄/TiO₂Heterojunction and Its Enhanced Photocatalytic Reduction of CO₂

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